Production of sulfitobetaines

ABSTRACT

PRODUCTION OF SULFITOBETAINES BY REACTION OF AMINES WITH 1,2-GLYCOL SULFITES AND THE NEW SULFITOBETAINES THEMSELVES. THE NEW PRODUCTS ARE VALUABLE STARTING MATERIALS FOR THE PRODUCTION OF DYES, DETERGENTS, WETTING AGENTS, FINISHES AND AUXILARIES IN THE TEXILE DYEING AND PRINTING FIELDS, AND FOR THE PRODUCTION OF PESTICIDES.

.yll t id ta es Patent 1, PRODUCTION. F SULFITOBETAINES Harry :Distler,:Ludwigsha'fen, and Rudi Widder, EppelhhQil iGermany,assignhrs toBadische Anilin- & Soda- Fabrik Alqrtiengesellschaft, Lupdwigshafen(Rhine), Gerrayving, Filed May 8, 1969, Ser. No. 823,160

,6 Claims priority, application Germany, May 10, 1968, 17 68 '407.0;'Aug."14,1968, P 17 93 191.8

- 260-401 9 Claims .-:ABSTRACT OF THE DISCLOSURE Production ofsulfitobetaines by reaction of amines with 1,2-glyiol siilfit'esand'the'new'sulfitobetaines themselves. The'n'ew products are valuable"starting materials for the production of dyes, -detergents, wettingagents, finishes and auxiliaries in the textile dyeing and printingfields, the'pr'o'dueti'onof pesticides.

' inventionrelates to the production of sulfito- "betaines by thereaction of airlines with 1,2-glycol sulfites anew the substances thusobtained.

z'ih-obiegitblt' this invention to provide a new process I'produ'c'tiomofsulfitobetaines in good yields and highpiirity u'sing"simple staItingmateriaIs.

Another object of the invention --is to provide new 'sulfit'obetaihes.'I'h'ese 'and 'other objects of the invention are achieved andsulfitobetaines"havingthe general formula:

Ra a

l ni'won-onosow where'the radicals R R R may be identical or differentand-each denotes an aliphatic, 'cycloaliphatic, araliphatic or, arouratic radical, individual radicals R and/or R may dense a hydrogen, atom,and R and one radical R or R and the pair of radicals R may togetherwith the adjacent nitrogen atom'be members of a heterocyclic ring;and/oraaltshaving the-general formula:

where R R and R have the above meanings are obmil edgadvantageously byreactingza-primary, secondary or tertiar amine'havingrthe generalformula:.

(III) where: l mania above meaningswith a 1,2-

glycolsulfite havingithe general formula:

" a 'Ra '11 (IJH mi- "o;s

"ice

When triethanolamine and 1,2-glycol sulfite are used, the reactlon maybe represented by the following equa- HOOHr-CH HOCHgCHgiN-CH2CH:O$O;Q

HOCH3CH3 l The process according to the invention surprisingly y elds alarge number of s'ulfitobetain'es (startingrfrom simple startingmaterials) in good yields and high purity. The amines used as startingmaterials and having the general Formula III may be primary,s'econdaryior tertiary. Preferred starting materials (III) andconsequently preferred end products (I) are those in whose formulae theindividual radicals R and R are identical or dilferent and each denotesan alkyl, a1kenyl, alkynyl, cycloalkyl,

, aralkyl or aryl radical having up to twenty-two, preferably up toeighteen, carbon atoms, or the radicals R may each denote a hydrogenatom, R and one'i'adical R or R and the pair of radicals R together withthe adjacent nitrogen atom may also be members of a saturated orunsaturated heterocyclic ring having three, five or six members whichmay contain, in addition to the nitrogen atom, an oxygen atom or anothernitrogen atom and which if desired may have a phenyl ring attachedthereto. The said radicals or the heterocyclic ring may bear (assubstituents) groups and/or atoms which are inert under the.

V dine and imidazole.

having up to eighteen, particularly up to twelve, p

reaction conditions, for example hydroxy groups, a1kyl groups having upto four carbon atoms, chlorine atoms, bromine atoms, sulfo groups, nitrogroups, or cyan'o groups. When mixtures of starting materials (III) areused, for example the palm oil amine mixture obtained by reaction ofdimethylamine with laur yl chloride and consisting substantially ofamines having twelve to fourteen carbon atoms, corresponding mixtures ofsuIfito betaines are obtained. For example the following amines may beused as starting materials (III): bntylamine;dodecylamine, cetylamine,stearylamine, cyclohexylamine, aniline, aor B-naphthylamine,benzylamine, allylamine, propargylamine, ethylenimine, diethylamine,diethanolamine, dibutylamine, di-(2-ethylhexyl)-amine, methyl aniline,diallylamine, methylbenzylamine, piperazine, trimethylamine,triethylamine, tributylamine, dimethyldodecylamine,dimethylstearylamine, distearylmethylamine, dimethylaniline,dimethylcyclohexylamine, triethanolamine, triisopropanolamine, pyridine,quinoline, quinal- Starting materials (III) include also primary,secondary or tertiary amines having the general Formula III in which theradicals R and R are identical or dilferent and one, two or all of theradicals R andR inayldenote' an alkyl radical bearing (as substituents)aliphaticHradicals on one or more carbon atomsxby way .of;;-groups'("J'O and/or -(fi -Nfl End products prepared from such startingmaterials (111) and having the Formula I and/or 11- have equivalentmeanings for R and R Preferred "starting materials (III) andconsequently preferredendproducts r(I r a lso, include those in Whoseformulae at least 'oneffandtpre erably one or two of the individualradicals 1 1? and? w J each denotes an alkyl radical having onetotwelve, particularly one to four, carbon atoms hearing (as asubstituent) an alkyl radical, alkenyl radical or alkynyl radical e herably up to four, carbon atoms attached to a carbon atom by way of agroup S,

The said radicals may also bear (as substituents) groups and/or atomswhich are inert under the reaction conditions, for example hydroxygroups, chlorine atoms, bromine atoms, nitro groups, sulfo groups, alkylgroups having up to four carbon atoms or cyano groups.

For example the following amines may be used as starting materials(III): N-stearylamidoethylpropylamine, N, N bis (stearylamidoethyl)propylamine, N-(stearylamidoethyl) N (acetamidopropyl) propylamine, N,N,N tris (laurylamidobutyl)-propylamine, N-isopropyllauratopropylamine,N,N bis (butylacetato)-propylamine, N ethylstearatoN,N-bis-(stearylamidoethyl)- propylamine, Nbutynylthiomethylpropylamine, N,N-bis- (propenylthiothyl) propylamine orN-(u,p-diacetato)- propylamine; corresponding amines bearing an allyl,butyl, cyclohexyl, phenyl or benzyl group as substituents on thenitrogen atom; N,N-diethanol-N-acetatoethylamine andN-ethylacetatopiperazine.

The strating material (HI) is reacted with a 1,2-glycol sulfite havingthe general Formula IV, generally in a stoichiometric amount. Thestarting amine (III), particularly in the case of a primary amine, mayalso be used in excess, for example in an excess of once to twice withreference to starting material (IV). The starting material (IV) may beprepared for example by reaction of ethylene oxide with sulfur dioxideby the method described in German Pat. No. 1,251,769.

Compounds which form 1,2-glycol sulfites during the reaction (forexample poly-1,2-glycol sulfites) may also be used for the reaction.Polyglycol sulfites are obtained for example by reacting ethylene oxidewith sulfur dioxide at 0 C.

Preferred starting materials (IV) and accordingly preferred end products(I) are those in whose formulae the individual radicals R are identicalor dilferent and each denotes a hydrogen atom or an alkyl, cycloalkyl,aralkyl or aryl radical having up to seven carbon atoms. The indiyidualradicals R may be identical to or difierent from the radical R and/orthe individual radicals R For example the following 1,2-glycol sulfitesmay be used as starting materials (IV): 1,2-glycol sulfite,1-methyl-1,2- glycol sulfite, 2-phenyl-1,2-glycol sulfite,1-cyclohexyl-l,2- glycol sulfite, 2-benzyl-1,2-glycol sulfite and1,2-dimethyl- 1,2-glycol sulfite.

Sulfitobetaines (I) prepared by the process according to the inventionmay be converted during the reaction or during processing of thereaction mixture into their salts having the general formula (H). As arule sulfitobetaines (I) are obtained as end products when tertiaryamines are used, the end product (I) or (H) or a mixture of the same,for example in the ratio of 1 mole of end product (I) to one mole of endproduct (II), is obtained when a secondary amine is used, and as a ruleend products (II) are obtained after the reaction mixture has beenworked up when primary amines are used.

The reaction is as a rule carried out at a temperature of from -10 to[+200 C., preferably from 20 to 150 C., at atmospheric orsuperatmospheric pressure, continuously or in batches. It isadvantageous to use a solvent which is inert under the reactionconditions such as water; alcohols, for example-methanol, butanol orcyclohexanol; aromatic hydrocarbons, for example benzene, toluene,xylene, nitrobenzene or chlorobenzene; ketones', for example acetone;chlorohydrocarbons, for example chloroform or ethylene chloride; ormixtures of the same. i

The reaction may be carried out as follows: a mixture of the startingmaterials (HI) and (IV) with or without from the reaction mixtureby aconventional. method, for example by filtration or fractionaldistillation.

The new compounds which can be prepared according to the process arevaluable starting materials for the production of dyes, detergents,wetting agents, finishes and auxiliaries for the textile dyeing .andprinting fields and also for the production of pesticides; For examplethe reaction product of N,N-distearyl-N-rnethylamine and glycol sulfiteor the end products of Examples'5 to ismay be used in an amount of from10 to. 40 grams per liter of aqueous finishing liquor for impregnating?cotton, rayon staple fiber or viscose cloth or appropriate yarnsfwhi'chare then dried so thata soft, smooth and full hand is imparted thereto.This treatment may be" combined with washing, wetting, finishing ordyeing yarns or cloth prepared therefrom, so that the products of theprocess in many cases also have a favourable infleunce on the other saidopertions. l

The invention is illustrated bythe following examples. The partsspecified in the examples are parts by weight.

EXAMPLE 1 A solution of 99 parts ofv cyclohexylamine and 20p'arts ofwater in 150 parts of methanol is slowly added to 54 parts of 1,2-glycolsulfite. After the mixture has been stirred for a short time a stronglyexothermic reaction-sets in and the temperature is kept at ow cooling.The colorless solid precipitated is suction'lfiltered 'and'recrystallized from alcohol. 150 parts (98.0%.of.t theory) of Ncyclohexyl N ethyl 8 sulfitocyclohexyl ammonium sulfite having a meltingpoint (with decomposition) of 305 C. is obtained. j

Analysis.Calculated for C H O N S (306), percent: C, 55.0; H, 9.8; O,15.7; N, 9.2; S, 10.3. Found (percent): C, 54.2; H, 10.2; 0, 15.6; N,9.9; S, 10.1. 1

EXAMPLE 2 A mixture of 121 parts of N-methylbenzylamine and 54 parts of1,2-glycol sulfite is heated to 80 C. while stirring. Five hours laterparts (96.0% of the theory) of N- methyl N benzyl N ethyl )3sulfitomethylbenzyl ammonium sulfite is obtained as a water-solubleyellow oil. n =L5534 1 s 1 Analysis-Calculated for C H gO N S (350),percent: C, 61.7; H, 7.45; O, 13.7; N, 8.0; S, 9.15. Found(pe'rcent):C, 61.4%;H, 7.7; O, 14.2; N, 6.8;S,9.5. f

EXAMPLE 3 A mixture of 74.5 parts of triethanolamine'an'd 54 parts ofglycol sulfite is stirred for five hours at 70 C. 119 parts (93.0% ofthe theory) of N-tris-fl-hydroxyethyl-flsulfitoethylbetaine is obtained.n =1;5211.

Analysis.-Calculated for CQH O NS (257), percent: C, 37.4; H, 7.4; O,37.4; N, 5.4; S, 12.45. Found (percent): C, 38.0; H, 7.9; O, 38.6; N,5.3 S, 11.7.

EXAMPLE 4..

53 parts of dimethyl palm oil amine. (prepared by reaction of 205 partsof lauryl chloride with 45: parts'of-dimethylarnine) and 27 parts ofpolyglycol sulfite are heated at C. while stirring in a stream ofnitrogen. After one hour the mixture is stirred for another four hoursat 90 C. so that a clear water-soluble yellow paste is formed. 75 parts(94.0% of the theory) of the sulfitobetaine of palm oil amine isobtained.

Analysis.'Calculated for C H O NS (321), percent: C, 60.0; H, 11.9;0,150; N, 4.3; S, 9.9. Found (percent): C, 58.9; H, 11.0; 0', 11.0;1N,3.8; S, 9.0..-:. .5"

(a) 1108 parts of stearic acid. is melted at 70? C; Under an atmosphereof nitrogen 290 parts of N-methyldipropyl- (a) 296 parts of methyl'stearate is melted at 50 C. under an atmosphere of nitrogen. 4 parts ofaluminum isopr'opylate and 89 parts of N,N-dimethylethanolamine areadded .while stirring. The mixture is heated up to 195 C. iii the courseof fifteen hours and at the same time the metlianoliormedis.distilledzotfiover a 20 cm. column with reflux. 333 3parts (93.5%.ofithetheory) of fl-N,N- dimethylaminoethyl stearateis obtained as ayellow oil.

. (bf) 89 partsof 3-N,N -dimethylaminoethylstearate has 27 partsofglycolsulfite'addedto it at 80 C. under nitrogen, and'the whole is stirredfOFjfiiKhQlllS at 110 C. The water-soluble .end. product isobtainedwhich crystallizes upon cooling.

. The;yield is 112 parts,=2(-9..6. 5,%= of; the theory) of N,N-dimethyl-N ethylstearato ,8 sulfitoethylbetaine. Melting point: 67 to 69C. (recrystallized from ethanol).

. 297 parts or, methyl stearate. 103, parts of N,N-dimethylari'olarnineand 6 partsof 'aIuminum isopropylate C i n tl'iefcour's 'of seven hoursas deo of the theory) of ethyl stearatens obtained as a yel- 103 partsof diethylenetriamine is added to 544 parts ltro'gen 'lfhe mixture isheated. in; the course bf nmet minutes to $175 ciand kept at thistemperature for five hours, the water of reaction fdr'med beingdistilled offQThe yield is 605 parts (97.5% of the theory) of startingmaterial (III). 158 parts of starting material (III) and 27 parts ofglycol sulfite are reacted for five hours at from 80 to 90 C. asdescribed in Example 2. The yield is' 183 parts (97.8% of the theory) ofN,N-bis-(stearamidoethyl)- 3 sulfitoethylbetaine; melting point from 85to87 16 .EXAMRLE9 596 parts of methyl stearate is melted and 204 partsof N,N dimethylpropylenediamine is added tothe meltunder nitrogen,The'reaction mixture is boiled uii der reflux for twofhours whilestirring and'then the methanol formed is distilled oil in the course ofsix hours with a rise intemper'a' N to 180 1C. Abrown viscous oilis'obtjaine'd which slo'wly' soliiiifiesiWhe"yield is" 730 parts (99.3%of the theory) of starting material (HI).

368 parts of starting material (III) is heated with 108 parts of glycolsulfite for two hours at 110 C. A crystalline brown product is formedupon cooling.

The yield is 470 parts (98.8% of the theory) of N,N-dimethyl-N-stearamidopropyl-B-sulfitoethylbetaine.

C H O N S (476).--Calculated (percent): C, 63.0; H, 10.9; 0, 13.45; N,5.88; S, 6.72. Found (percent): C, 62.5; H, 11.0; 0, 14.6; N, 5.9; S,6.3.

EXAMPLE l0 200 parts of lauric acid is melted under nitrogen. 134 partsof N,N-dimethylethanolamine is added while stirring and the mixture isheated to C. Four hours later the water of reaction begins to distil offthrough a descending condenser, and the temperature rises in the courseof twelve hours to from to 200 C. 268 parts (99.0% of the theory) of,B-N,N-dimethylaminoethyl laurate is obtained in the form of a brownoil.

162 parts of B-N,N-dimethylaminoethyl laurate is stirred with 65 partsof glycol sulfite for four hours at 80 C. 220 parts (96.8% of thetheory) of N,N-dimethyl-N- ethyllaurato-;8-sulfitoethylbetaine isobtained in the form of a yellow paste.

C18H37O5NS (379).Calculated (percent): C, 57.1; H, 9.75; O, 21.1; N,3.7; S, 8.43. Found (percent): C, 57.7; H, 10.2; 0, 21.4; N, 3.6; S,6.5.

300 parts of lauric acid and 154 parts of N,N-dimethyl isopropanolamineare reacted as described in Example 6. The yield is 384 parts offl-N,N-dimethylaminoisopropyl laurate in the form of a red oil.

142 parts of fi-N,N-dimethylaminoisopropyl laurate and 54 parts ofglycol sulfite are stirred for four hours at from 100 to 130 C. A brownviscous oil is obtained. The yield is parts (96.8% of the theory) ofN,N-dimethyl-N- isopropyllaurato-p-sulfitoethylbetaine. n 1.4654.

282 parts of oleic acid and 102 parts of N,N-dimethylamine are condensedat 150 C. as described in Example propylenediamine are reacted at 260 C.in the course of 6. 1100 parts (99.2% of the theory) offl-N,N-diethanoltwelve hours as described in Example 6. The yield is 35510 aminoethyl stearate is obtained. 1 parts (97.1% of the theory) ofoleic acid (gamma-N,N- 207 parts of fi-N,N-diethanolaminoethyl.stearateand dimethylamino)-propylamide in the form of a brownoil. 54 parts ofglycol sulfite are reacted for fifteen hours at 183 parts of oleic acid(gamma-N,N-dimethylamino)- 95 C. while stirring. 254 parts (97.3% of thetheory) of propylamide and 54 parts of glycol sulfite are reacted atN,N-diethanolaminoN-ethylstearato-fi-sulfitoethylbetaine 100 C. for fivehours while stirring. 230 parts (97.0% is obtained in the form of ayellow solid product.

of the theory) of N,N-dimethyl-N-oleamidopropyl-fi-sulfitoethylbetaineis obtained in the form of a brown paste. EXAMPLE 18 C H O N S(474).-Calculated (percent): C, 63.3; CH; H, 10.55; N, 5.9; s, 6.74.Found (percent): 0, 63.2; H, ommrsficHiggwfircflrmsom 10.7; N, 5.5; S,5.9. 20 1 422 parts of oleic acid and 134 parts of N,N-dimethyl- 62parts of the thioether prepared from dodecylmerethanolamine are reactedat a temperature of 170 C. as captan, formaldehyde and dimethylamine bythe process described in Example 6. The yield is 496 parts (99.1% ofdescribed in German Pat. No. 820,005 and 26 parts of the theory) of.fl-N,N-dimethylaminoethyl oleate in the glycol sulfite are reacted foreight hours at 100 C. while form of a red oil. 30 stirring. 81 parts(94.3% of the theory) of N,N-dimethyl- 141 parts of,B-N,N-dimethylaminoethyl oleate and 43N-dodecylthiomethyl-fl-sulfitoethylbetaine is obtained in parts ofglycol sulfite are reacted at 100 C. for six hours the form of ayellowish paste. 11 11.4735.

while stirring. 454 parts (98.5% of the theory) of N,N-di- What we claimis: methyl-N-ethyloleato-;8-sulfitoethylbetaine is obtained in 1. Aprocess for the production oi sulfitobetaines havthe form of a yellowwater-soluble paste. 3 5 ing the general formula:

C24H4705NS ).-Calculatcd (percent): C, H, R2 R3 5 10.7; 0, 17.3; N,3.00; S, 6.90. Found (percent): C, 63.9; 9 (+11 1 I H, 10.7; 0, 17.0; N,2.8; s, 5.1.

EXAMPLE 15 CH3 CH3 422 parts of oleic acid and 154 parts ofN,N-dimethyl- 45 Where individual a s R R and R may be identicalisopropanolamine are reacted at a temperature of 170 difiefel'lt andeach denotes an aliphatic, cycloaliphatic, C. as described in Example 6.The yield is 500 parts araliphatic or aromatic radical, the individualradicals R (90.8% of the theory) of a-N,N-dimethylaminoisopropyl and/ orR may also each denote a hydrogen atom, and/ oleate. or salts having thegeneral formula: V

183 parts of a-N,N-dimethylaminoisopropyl oleate and 54 parts of glycolsulfite are reacted for six hours at 140 Ra Ra C. while stirring. A redwater-soluble oil is obtained. The l: I l I 1 yield is 230 parts 97.0%of the theory) of N,N-dimethy1-N-isopropyloleato-fi-sulfitoethylbetaine. n =1.4727. 55

EXAMPLE 16 where R R and R have the above meanings, wherein(CnHzz-CONHCH2CH2CH2)2- 1?CH2CH2OSOz a p y, secondary or tertiary aminehaving tha g CH1 eral formula:

400 parts of lauric acid and 145 parts of N-methyldipropylenetriamineare reacted analogously to Example 4. i The condensation product isrecrystallized from alcohol. The yield is 500 parts (98.2% of thetheory), M.P. In 724? c. R1

204 parts of 'the condensation product of lauric acid 05 1 andN-methyldipropylenetriamine and 43 parts of glycol I sulfite are reactedfor six hours at 130 C. while stirring. where R1 and R2 have the abovemeanmgs 1S reacted 241 parts (97.6% of the theory) ofN-methyl-N,N-biswith lzl'glvycol sulfite having the general m llauramidopropyl)-B-sulfitoethylbetaine is obtained in the form of ayellow water-soluble paste. I

EXAMPLE 17 CH'F"OH2OH I 'i CHFCHQTOH where R has the above meaning.

2. A sulfitobetaine having the general formula:

where the individual radicals R R and R may be identical or dilferentand each denotes an aliphatic, cycloaliphatic or aromatic radical, andthe individual radicals R and/or R may also denote a hydrogen atom.

3. A salt having the general formula:

5. A process as claimed in claim 1 wherein at least one of theindividual radicals R and R in its meaning as an 10 aliphatic radicalrepresents in the end products (I) and/ or (II) and in the startingmaterial (III) an alkyl radical bearing an aliphatic radical as asubstituent attached by way of one of the groups S-,

'CO and/or --CNH 6. A process as claimed in claim 1 carried out with apoly-1,2-glycol sulfite as starting material (IV).

7. A process as claimed in claim 1 carried out at a temperature of from1() C. to +200 C.

8. A process as claimed in claim 1 carried out at a temperature of from20 C. to 150 C.

9. A process as claimed in claim 1 carried out in the 15 presence of aninert solvent.

References Cited UNITED STATES PATENTS 3,225,073 12/ 19 65 Leverkusen etal. 260-401 20 3,280,179 10/r1966 Ernst 260'501 ELBERT L. ROBERTS,Primary Examiner US. Cl. X.R.

- 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent-No.5,641,072 Dated February 8, 1972 or) Harrv Distler and Rudi widder Itis, certified that error appeare in'the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 1, lines 66-71, Ili Ill should read ---'R3 R3 HC H H? on os -oo-sl-o Column 2, lines 5-8, HOCH -CH CIJH -(IZH should read HoCHg-fHg(fHg-fI-Iz Column 5, line 25, "strating" should read starting Column 6,line 63, that portion of the formula reading "CH2-CH3CH2" ShOUld. readCH2-CII2CH2 Column 9, line 2, claim 2, Ft R R should read Signed andsealed this 18th day of July 1972-.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Y Commissionerof Patents

